Agricultural fluid deposition aid

ABSTRACT

A deposition aid is provided, comprising a low molecular weight, low viscosity polysiloxane, combined with a crop oil concentrate or esterified seed oil concentrate. Combinations including the modified silicone can improve spreading and/or adhesion to foliage. Adding about 5% to about 20% of the modified silicone can provide more than a proportional increase in spreading and/or adhesion.

FIELD OF THE INVENTION

The invention relates generally to additives that can improve thedeposition properties of certain fluids, and more particularly toformulations and methods for improving the deposition properties offluids that are sprayed onto plant surfaces for agricultural purposes.Compositions in accordance with the invention are particularly usefulwith agrochemicals, more particularly with herbicides, insecticides,fungicides, biologicals and growth regulators.

BACKGROUND OF THE INVENTION

Many chemical formulations benefit from the inclusion of surfactants.For example, including certain surfactants in a chemical formulation canefficiently reduce the surface tension of the formulation. This canimprove the ability of the formulation to adhere to the surface to whichit is applied and for the same amount of the formulation to spread overa larger area of the surface. Therefore, in agriculture, adding thecorrect surfactants can promote improved adherence of the formulation tothe plant to which it is applied and can help the same amount of anagrochemical formulation to cover a larger area of the plant.

Emulsifiable petroleum oils (crop oil concentrates or COCs) andemulsifiable methylated seed oils (MSOs) have long been used asagricultural spray adjuvants to enhance the performance of systemicpesticides and other agricultural chemicals. Crop oil concentrates andmethylated seed oil concentrates generally contain surfactant packagesthat are designed to aid in emulsification and deposition properties.These oils are typically used to enhance the application and penetrationof agricultural chemicals into plants, fungi and insects. Thesurfactants, in addition to oil emulsification, can improve spraydeposition properties by reducing the surface tension of the dispersionor emulsion and thereby enhance droplet adhesion on foliar surfaces. Asused herein, the term surfactant will include emulsifiers, dispersantsand spreaders that affect the surface tension of compositions to whichthey are added.

However, it is desirable to further improve the spreading, adhesion andother properties of agricultural chemicals that include COCs and MSOs.Accordingly, an adjuvant composition is desirable that can improve theadhesion and spreading properties of agricultural pesticides beyond whatis attainable using the prior art.

SUMMARY OF THE INVENTION

Generally speaking, in accordance with the invention, a spreading anddeposition aid is provided. The aid can comprise a polysiloxane, such asa polydimethylsiloxane, an oil, and a surfactant. Low viscositypolysiloxanes having a low molecular weight are preferred, e.g., thosehaving a molecular weight (as used herein, the molecular weight ofsilicone oils will refer to the number average molecular weight of thoseoils) below about 5000 g/mole, preferably below about 4000 g/mole, andmore preferably, below about 2,000 g/mole. Preferred polysiloxanes havea kinematic viscosity below about 100 centistokes (cSt) at 25 degreesC., preferably below about 50 cSt at 25 degrees C., and more preferablybelow about 20 cSt at 25 degrees C. (ASTM D 445). Agriculturalcompositions in accordance with the invention can comprise a bioactivematerial in combination with the spreading and deposition aid discussedherein, comprising a polysiloxane component, an oil component, and asurfactant. Agricultural compositions in accordance with the inventioncan include crop oil concentrates (COCs) or methylated seed oilconcentrates (MSOs). They can comprise 20% or less, preferably 10% orless of the polysiloxane. In these compositions, the polysiloxane servesto significantly improve the adhesion and/or spreading of the sprayedagricultural composition droplets on vegetation when compared totraditional COC and MSO containing compositions. The ratio of carbon tosiloxane in these polysiloxanes should be sufficient to render themsoluble or dispersible in the oil base stock.

An organosilicone-based agricultural composition for agricultural use inaccordance with the invention can include a combination of (a) an oilcomponent, (b) a surfactant; and (c) about 1% to 95% of a polysiloxanehaving a molecular weight below about 5,000, preferably below about4,000 g/mole and a viscosity below about 100, preferably below about 50cSt at 25° C., wherein the polysiloxane is soluble or dispersible in theoil component.

Compositions in accordance with the invention can increase the spreadingor adhesion properties of an agricultural formulation when compared tothe same formulation, but in the absence of the polysiloxane ororganomodified polysiloxane.

The oil of this invention may be a petroleum oil, paraffinic oil,mineral oil, vegetable oil and/or esterified vegetable oil (e.g.,methylated seed oil, methyl soyate, methylated rapeseed oil, methylatedcottonseed oil, methylated palm oil, methylated corn oil) includingnaturally derived or synthetically prepared methyl, ethyl, propyl andisopropyl esters of C8 to C18 fatty acids, (e.g., isopropylmyristate,methyl oleate, ethyl oleate and methyl palmitate). The surfactant,dispersant and/or spreader of the deposition aid of this invention caninclude at least one surfactant derived from the ethoxylation oralkoxylation of primary or secondary alcohols. This includes surfactantsselected from polyoxyethylene, polyoxypropylene, polyoxybutylene, andmixed polyalkyleneoxide alkoxylates of fatty alcohols. The surfactantsmay also include trisiloxane alkoxylates, alkyne diol alkoxylates, andblocked or random polyoxyethylene/polyoxypropylene copolymers.

Optionally the composition may also contain a solvent selected fromd-limonene, triacetin, isopropylmyristate, esterified seed oil; or othersuitable solvents.

BRIEF DESCRIPTION OF THE DRAWINGS

For a fuller understanding of the invention, reference is had to thefollowing description, taken in connection with the accompanyingdrawings, in which:

FIG. 1 is a graph showing examples of the equilibrium surface tension ofmineral oil/silicone oil mixtures;

FIG. 2 is a graph showing examples of the equilibrium surface tension ofmixtures of OSIL-1 in MO-1;

FIG. 3 is a graph showing examples of the equilibrium surface tension ofmethyl soyate/silicone oil mixtures;

FIG. 4 is a graph showing examples of the effects of PDMS addition onthe Dynamic Surface Tension (DST) of COCs;

FIG. 5 is a graph showing spread diameters of 0.5% dispersions in twoexamples;

FIG. 6 is a graph showing emulsion stability in two examples;

FIG. 7 is a graph showing examples of the effect of low MW PDMS on thefoam volume of MSO adjuvants containing organosilicone superspreaders;

FIG. 8 is a graph showing examples of the equilibrium surface tension ofAlkyl-Silicone/MO-1 Blends;

FIG. 9 is a graph showing examples of the droplet adhesion on poinsettialeaves among example formulations; and

FIG. 10 is a graph showing examples of the effect of PDMs on DynamicSurface Tension of COCs.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

In the specification and claims herein, the following terms andexpressions are to be understood as indicated.

The singular forms “a,” “an,” and “the” include the plural, andreference to a particular numerical value includes at least thatparticular value, unless the context clearly dictates otherwise.

Other than in the working examples or where otherwise indicated, allnumbers expressing amounts of materials, reaction conditions, timedurations, quantified properties of materials, and so forth, stated inthe specification and claims are to be understood as being modified inall instances by the term “about”.

All methods described herein may be performed in any suitable orderunless otherwise indicated herein or otherwise clearly contradicted bycontext. The use of any and all examples, or exemplary language (e.g.,“such as”) provided herein, is intended merely to better illuminate theinvention and does not pose a limitation on the scope of the inventionunless otherwise claimed.

No language in the specification should be construed as indicating anynon-claimed element as essential to the practice of the invention.

The terms, “comprising,” “including,” “containing,” “characterized by,”and grammatical equivalents thereof are inclusive or open-ended termsthat do not exclude additional, unrecited elements or method steps, butwill also be understood to include the more restrictive terms“consisting of” and “consisting essentially of.”

It will be understood that any numerical range recited herein includesall sub-ranges within that range and any combination of the variousendpoints of such ranges or sub-ranges.

As used herein, integer values of stoichiometric subscripts refer tomolecular species and non-integer values of stoichiometric subscriptsrefer to a mixture of molecular species on a molecular weight averagebasis, a number average basis or a mole fraction basis.

It will be further understood that any compound, material or substancewhich is expressly or implicitly disclosed in the specification and/orrecited in a claim as belonging to a group of structurally,compositionally and/or functionally related compounds, materials orsubstances includes individual representatives of the group and allcombinations thereof.

The term “agrochemical,” or “agricultural chemical,” as used hereinshall be understood to refer to all bioactive compounds, biologicalmaterials including extracts, fractions and by-products thereof, livingorganisms including microorganisms, and the like, that are suitable foragricultural use such as pesticides, herbicides, fungicides,insecticides, nematocides, larvacides, mitocides, ovacides, plant growthregulators, seed treatment agents, etc. “Agricultural composition”refers to a composition that is applied to plants, weeds, landscapes,grass, trees, pastures, or for other agricultural applications.Agricultural compositions can be provided in concentrated or dilutedform. An agricultural composition may or may not contain an agrochemical(agricultural chemical).

The term “adjuvant” as used herein includes optional components thatimpart a functionally useful property to a composition, e.g.,dispersing, wetting, spreading, etc., and/or enhances a functionallyuseful property already possessed in some degree by the composition,including any composition, material or substance which increases theefficacy of the agrochemical or active material to which it is added.

The term “bioactive” refers to an agricultural chemical or materialhaving biological activity, i.e., a positive or negative effect on aliving (plant, animal, bacterial or protozoan) organism, including butnot limited to pesticides, e.g., herbicides, fungicides, insecticides,acaricides and molluscides; plant or animal nutrients; defoliants; and,plant or animal growth regulators.

The expression “hydrocarbon group” or “hydrocarbon radical” means anyhydrocarbon from which one or more hydrogen atoms has been removed andis inclusive of alkyl, alkenyl, alkynyl, cyclic alkyl, cyclic alkenyl,cyclic alkynyl, aryl, aralkyl and arenyl groups and is inclusive ofhydrocarbon groups containing at least one heteroatom.

The term “alkyl” means any monovalent, saturated straight, branched orcyclic hydrocarbon group; the term “alkenyl” means any monovalentstraight, branched, or cyclic hydrocarbon group containing one or morecarbon-carbon double bonds where the site of attachment of the group canbe either at a carbon-carbon double bond or elsewhere therein; and, theterm “alkynyl” means any monovalent straight, branched, or cyclichydrocarbon group containing one or more carbon-carbon triple bonds and,optionally, one or more carbon-carbon double bonds, where the site ofattachment of the group can be either at a carbon-carbon triple bond, acarbon-carbon double bond or elsewhere therein. Examples of alkylsinclude methyl, ethyl, propyl and isobutyl. Examples of alkenyls includevinyl, propenyl, allyl, methallyl, ethylidenyl norbornane, ethylidenenorbornyl, ethylidenyl norbornene and ethylidene norbornenyl. Examplesof alkynyls include acetylenyl, propargyl and methylacetylenyl.

The term “superspreader” as used herein refers to those adjuvantsurfactants that have the property of “superspreading”, or“superwetting”. Superspreading/superwetting is the ability of a drop ofa solution of a superspreader surfactant to spread to a diameter that isgreater than the diameter of a drop of distilled water on a hydrophobicsurface, and also greater than the diameter to which a solution of waterand non-superspreading surfactant spreads on the hydrophobic surface.

The term “tank-mix” means the combination of at least one agrochemicalwith a spray medium, such as water or oil, at the point of use(application). The term “In-can” refers to a formulation or concentratecontaining at least one agrochemical component. The “In-can” formulationmay then be diluted to its application concentration at the point ofuse, typically in a tank-mix, or it may be used undiluted.

Crop oil concentrates (COCs) and methylated seed oils (MSOs) are classesof agricultural adjuvants that are based on petroleum oil and seed oilbase stocks respectively. The COCs and MSOs contain surfactant packagesthat typically make up 5 to 40 percent of the product's composition.COCs and MSOs are sold neat and then diluted with water by the end-userbefore spraying. The surfactant packages act to disperse or emulsify theoil phase into the water, and to help the deposition (adhesion) andspreading of the sprayed emulsion or dispersion onto the target surface.COCs and MSOs can enhance the penetration of systemic pesticides andother agrochemicals into the plants, fungi and insects to which they areapplied.

It has been determined that the addition of low molecular weightpolysiloxanes (e.g. silicone oils) in accordance with the invention canfurther reduce the surface tension of the petroleum oil and seed oilbase stocks that are used to make COCs and MSOs. The benefits (e.g.,improved droplet adhesion, spreading, and/or emulsion stability)imparted to the COCs and the MSOs, and the resulting agriculturalcompositions containing these COCs and MSOs by the addition of thepolysiloxane, can surprisingly exceed those expected from theagricultural formulations alone, i.e. without the polysiloxanes.

It was surprisingly determined that the sprayed droplets of theformulations containing the polysiloxanes had improved adhesion to plant(e.g., leaf) surfaces even where there was no associated reduction inthe dynamic surface tension of the respective formulations. Furthermore,the high spreading of the emulsions described herein along with improvedemulsion stability was also quite surprising.

Spreading and deposition aids in accordance with the invention can beformed by combining the following components: (a) 5% to 95%, preferably50% to 90% of an oil component, (b) 1% to 50%, preferably 5% to 20% ofan emulsifier, surfactant, dispersant or superspreader component; and(c) about 1% to 95%, preferably 2% to 20% and more preferably, 5% to 15%of a polysiloxane having a low molecular weight. Preferred polysiloxaneshave a molecular weight of about 5000 g/mole or lower, preferably about4000 g/mole or lower, more preferably 2000 g/mole or lower. Thepolysiloxane should have a viscosity below about 50 cSt, preferablybelow about 20 cSt at 25° C. The polysiloxane should be soluble ordispersible in the oil component. Preferred agricultural compositions inaccordance with the invention can spread on or adhere to a leaf surfaceat least 10% better, preferably more than 20% better and more preferablyat least 50% better than the same formulation will spread or adhere inthe absence of the polysiloxane.

The oil component can be a mineral oil, a paraffinic crop oil, avegetable oil, or an esterified seed oil and the polysiloxane is apolydimethylsiloxane or an organo-modified polysiloxane. Preferred oilcomponents include: mineral oil, paraffinic oil, seed oil, soybean oil,corn oil, canola oil, rapeseed oil, sunflower oil, palm oil, cottonseedoil, methylated seed oil, methylated soybean oil, methylated rapeseedoil, methylated cotton seed oil, methylated corn seed oil, partiallymethylated seed oil, partially methylated soybean oil, methyl caprylate,methyl laurate, methyl myristate, methyl palmitate, methyl oleate, andmethyl stearate.

Compositions of the invention can optionally be combined with one ormore other adjuvant components known for incorporation in aqueousagricultural sprays. Among the many kinds of optional adjuvant aresurfactants of both the organosilicon and non-organosilicon types andantifoam additives and additives like stickers, thickeners, dyes, and soforth.

Acceptable emulsifiers and surfactants include: nonionic, anionic,cationic and zwitterionic surfactants. Non-limiting examples of suitablenonionic surfactants include alcohol ethoxylates, alkylpolyglycosides,alkyleneoxide copolymers of ethyleneoxide with propyleneoxide,butyleneoxide, alkylpolyglycerols, acetylenic diol alkoxylates, and thelike. Non-limiting examples of suitable anionic surfactants includealkylsulfates (e.g., sodium lauryl sulfate, sodium laurylethoxy sulfatesand 2-ethylhexylsulfate), alkylbenzene sulfonates (e.g., sodiumdodecylbenzene sulfonates), C8-C18 phosphate, mono-, di- and tri-esterswith alkyleneoxide, alkyl sarcosinates such as sodium laurylsarcosinate, and the like. Non-limiting examples of suitable cationicsurfactants include C8-C18 alkoxylated fatty amines and imidazolines.Non-limiting examples of suitable zwiterionic surfactants include C8-C18amidopropyl betaines, such as, but not limited to, lauryl betaine,myristyl betaine, lauramidopropyl betaine, soyamidopropyl betaine,laurylamido betaine, oleyl betaine, lecithins and the like. Theagricultural composition can preferably include a fatty alcoholalkoxylate surfactant, e.g., polyoxyethylene, polyoxypropylene,polyoxybutylene, and mixed polyalkyleneoxide alkoxylates of fattyalcohols. Surfactants having short chain hydrophobes that do notinterfere with superspreadingare described in U.S. Pat. No. 5,558,806,the entire contents of which are incorporated by reference herein, arealso useful.

Specific acceptable examples include isodecyl alcohol ethoxylates(Alkosynt ID 30, Oxiteno, Rhodasurf DA 530, Solvay, Ethal DA-4, Ethox),isotridecyl alcohol ethoxylates (Genapol X 050, Genapol X 060, Genapol X080, Clariant, Alkosint IT 60, Alkosint IT 120, Oxiteno), tridecylalcohol ethoxylates (Lutensol TDA 6, Lutensol TDA 9, Lutensol TDA 10,BASF), guerbet alcohol alkoxylates (Lutenxol XL 50, Lutensol XP 50,Lutensol XL 60, Lutensol XP 60, Lutensol XL 80, Lutensol XP 80, BASF),secondary alcohol ethoxylates (Tergitol 15-S-3, Tergitol 15-S-5,Tergitol 15-S-7, Tergitol 15-S-9, Dow Chemical), polyethylene glycoltrimethylnonyl ether (Tergitol TMN 3, Tergitol TMN 6, Tergitol TMN 10,Dow Chemical) alkyl acetylenic diols (Surfynols, Air Products),pyrrilodone based surfactants (e.g., Surfadone LP 100, Ashland), 2-ethylhexyl sulfate, ethylene diamine alkoxylates (Tetronics, BASF), ethyleneoxide/propylene oxide copolymers (Pluronics, BASF), gemini-typesurfactants (Rhodia/Solvay) and diphenyl ether gemini-type surfactants(DOWFAX, Dow Chemical

Preferred solvents include: isopropyl myristate, d-limonene, citrusterpene oil, or triacetin.

Preferred superspreaders include: siloxane polyalkyleneoxide copolymers.Non-limiting examples include polyoxyethylene, polyoxypropylene,polyoxybutylene, and mixed polyalkyleneoxide alkoxylates oftrisiloxanes, tetrasiloxanes and pentasiloxanes.

Polysiloxanes in accordance with the invention can have the generalformula (I), (II) or (III), below. The most preferred polysiloxanes arelow viscosity polysiloxanes, e.g., up to 20 cSt, and/or up to an averageMW of 2000 g/mol. Of the three formula, most preferred is generalformula (I), especially with viscosities equal to or below about 20cSt.:

M ¹ D _(x) D ¹ _(y) M ²  (I)

wherein:

-   -   M¹=R¹R²R³SiO_(1/2)    -   M²=R⁴R⁵R⁶SiO_(1/2)    -   D=R⁷R⁸SiO_(2/2)    -   D¹=R⁹R¹⁰SiO_(2/2)    -   R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from a        monovalent alkyl hydrocarbon radical of 1 to 18 carbons, and        aryl or alkaryl hydrocarbon radicals of 6 to 14 carbon atoms;    -   R⁷ and R⁸ are independently selected from monovalent hydrocarbon        radicals of 1 to 4 carbon atoms;    -   R⁹ and R¹⁰ are independently selected from a monovalent        hydrocarbon radical of 1 to 18 carbons, and aryl or alkaryl        hydrocarbon radicals of 6 to 14 carbon atoms; and    -   subscripts x and y are independently 0 to 50, with the proviso        that x+y is about 1 to 50.

Preferred structures of Formula (I) are those wherein Y=0 and all the Rgroups are methyl and the viscosity is 50 cSt or lower at 25 deg C.,preferably 20 cSt or lower at 25 deg C. Other preferred examples ofFormula I include those: wherein x+y is 5 to 50; wherein y=0 and x is 3to 50; wherein R¹ to R⁸ are methyl; wherein y=0, x=3 to 50, and R¹ to R⁸are methyl; wherein y=0 and x is about 5 to 25 and R¹ to R⁸ are methyl;wherein R¹⁰ is a monovalent alkyl hydrocarbon radical of 1 to 18carbons, or an aryl or alkaryl hydrocarbon radical of 6 to 14 carbonatoms and R¹ through R⁹ are methyl; wherein Wand R⁴ are monovalent alkylhydrocarbon radicals of 1 to 18 carbons or aryl or alkaryl hydrocarbonradicals of 6 to 14 carbon atoms and R², R³, and R⁵ through R¹⁰ aremethyl; wherein R¹⁰ is a monovalent alkyl hydrocarbon radical of 1 to 18carbons, or an aryl or alkaryl hydrocarbon radical of 6 to 14 carbonatoms; or wherein R¹ through R⁹ are methyl.

Polysiloxanes in accordance with this invention can also be defined bystructure (II)

TS ¹ R ¹¹ TS ²  (II)

wherein,

-   -   TS¹ and TS² are independently        R¹²R¹³R¹⁴Si—O—Si^(a)(R^(A))—O—SiR¹⁵R¹⁶R¹⁷

wherein

-   -   Si^(a) is a monovalent radical and R¹¹ attaches to Si^(a)    -   R¹¹ is selected from divalent hydrocarbon radicals of 4 to 18        carbons,    -   R^(A), R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are independently        selected from monovalent hydrocarbon radicals of 1 to 4 carbons.

Preferred examples of formula II include examples wherein R^(H) is adivalent hydrocarbon radical containing 4 to 18 carbons and whereinR^(A) and R¹² through R¹⁷ are methyl (—CH₃) groups.

Polysiloxanes in accordance with this invention can also be defined bystructure (III)

R¹⁹—[Si(CH₃)₂O_(1/2)-(D ²)z-O_(1/2)Si(CH₃)₂—R¹⁸]_(w)—R²⁰  (III)

wherein

-   -   R¹⁹=H—, CH₃—, or HR¹⁸—    -   R²⁰=H—, or —Si(CH₃)₂O_(1/2)-(D²)z-O_(1/2)Si(CH₃)₂H or        —Si(CH₃)₂O_(1/2)-(D²)z-O_(1/2)Si(CH₃)₂CH₃,    -   R¹⁸ is selected from divalent hydrocarbon radicals of 4 to 18        carbons D²=R²¹R²²SiO_(2/2),    -   R²¹ and R²² are independently selected from monovalent        hydrocarbon radicals of 1 to 4 carbons,    -   z=2 to 20, and    -   w=1 to 20 (w=1 or 2 is preferred).

Preferred examples of formula III include examples where w=1-10 andwherein R²¹ and R²² are methyl (—CH₃) groups.

The agricultural composition can preferably include a solvent selectedfrom d-limonene, triacetin, isopropylmyristate, and esterified seed oil.

A method in accordance with the invention involves increasing thespreading and/or adhesion properties of an agricultural compositioncontaining a mineral oil, a paraffinic crop oil, esterified seed oil ora vegetable oil, including COCs and MSOs, comprising adding to theagricultural composition, an effective amount of a selected polysiloxaneor organo-modified polysiloxane having an average molecular weight belowabout 5000 g/mole, preferably below about 4000 g/mole, and morepreferably, below about 2,000 g/mole. Preferred polysiloxanes have akinematic viscosity below about 100 centistokes (cSt) at 25 degrees C.,preferably below about 50 cSt at 25 degrees C., and more preferablybelow about 20 cSt at 25 degrees C. (ASTM D 445). Preferredpolysiloxanes have general formulae I, II or III, identified above. Themethod can be effective to cause the composition to exhibit improvedadhesion and/or spreading when compared to the same composition, but inthe absence of the polysiloxane or organomodified polysiloxane.Increases of over 10%, 20% and even 50% improved spreading and/oradhesion are possible.

Deposition aids in accordance with the invention can be provided as anagricultural composition, blended on site from individual components, ora combination thereof. For example, they can be provided as isolatedpolysiloxanes or combined with other materials such as mineral oils,vegetable oils, esterified seed oils, surfactants and agrochemicals toform a tank mix, which can then be applied as desired.

Optimal amounts of the polysiloxane spreading and deposition aid for aspecific spray composition and spraying operation can be readilydetermined employing routine experimental testing procedures known inthe art. For many spray compositions, amounts of the compositions ofthis invention ranging from 0.01 to 5, and preferably from 0.05 to 1weight percent can be incorporated therein with generally good spreadingand adhesion results. Accordingly, the invention comprises an MSO and/orCOC containing a polysiloxane as described herein, preferably at aconcentration of 1-20% in the MSO or COC. The MSO or COC can then bediluted with water for agricultural purposes by the end user to make anemulsion or spray solution. The MSO or COC will typically make up 0.1 to2 percent of this end use emulsion or spray solution.

Agricultural sprays, in addition to the compositions of the invention,can include one or more known and conventional active ingredients oragrochemicals of agricultural compositions, such as pesticides,fertilizers, and micronutrients.

Pesticidal sprays include at least one pesticide. Optionally, thepesticidal spray may include excipients, surfactants, solvents, foamcontrol agents, deposition aids, biologicals, micronutrients,fertilizers, and the like. The term “pesticide” means any compound thatis used to destroy pests, e.g., rodenticides, insecticides, miticides,acaricides, fungicides, herbicides, and so forth. Illustrative examplesof pesticides that can be employed include, but are not limited to,growth regulators, photosynthesis inhibitors, pigment inhibitors,mitotic disrupters, lipid biosynthesis inhibitors, cell wall inhibitors,and cell membrane disrupters. The amount of pesticide employed in aspray composition will vary with the particular type of pesticide.

Specific examples of herbicidal and plant growth regulator compoundsthat can be incorporated in a spray composition include, but are notlimited to: phenoxy acetic acids, phenoxy propionic acids, phenoxybutyric acids, benzoic acids, triazines and s-triazines, substitutedureas, uracils, bentazon, desmedipham, methazole, phenmedipham,pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines,isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin,glyphosate, sulfonylureas, imidazolinones, clethodim, diclofop-methyl,fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop,sethoxydim, dichlobenil, isoxaben, bipyridylium compounds, and the like.Common and Chemical Names of Herbicides Approved by the Weed ScienceSociety of America, Weed Science, 58:511-18 (2010) is incorporatedherein by reference.

Specific examples of fungicidal compositions include, and are notlimited to, aldimorph, tridemorph, dodemorph, dimethomorph; flusilazol,azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole,tebuconazole and the like; imazalil, thiophanate, benomyl carbendazim,chlorothialonil, dicloran, trifloxystrobin, fluoxystrobin,dimoxystrobin, azoxystrobin, furcaranil, prochloraz, flusulfamide,famoxadone, captan, maneb, mancozeb, dodicin, dodine, metalaxyl, and thelike.

Specific examples of insecticide, larvacide, miticide and ovacidecompounds that can incorporated in the aqueous spray compositionsinclude, but are not limited to, Bacillus thuringiensis (or Bt),spinosad, abamectin, doramectin, lepimectin, pyrethrins, carbaryl,primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform,novaluron, bistrifluoron, triflumuron, diflubenzuron, imidacloprid,diazinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl,azinphos-methyl, izoxathion, chlorpyrifos, clofentezine,lambda-cyhalothrin, permethrin, bifenthrin, cypermethrinrn, and thelike.

Fertilizers and micronutrients include, but are not limited to, zincsulfate, ferrous sulfate, ammonium sulfate, urea, urea ammoniumnitrogen, ammonium thiosulfate, potassium sulfate, monoammoniumphosphate, urea phosphate, calcium nitrate, boric acid, potassium andsodium salts of boric acid, phosphoric acid, magnesium hydroxide,manganese carbonate, calcium polysulfide, copper sulfate, manganesesulfate, iron sulfate, calcium sulfate, sodium molybdate, calciumchloride, and the like.

Buffers, preservatives and other standard agricultural excipients knownin the art may also be included in the spray composition.

Agricultural spray compositions may be made by combining in anycombination and/or sequence in a manner known in the art, such as mixingin water, one or more of the above spray components and the compositionsof the present invention, either as a tank-mix, or as an “In-can”formulation.

The invention also comprises agricultural compositions of thisinvention, applied to and used to treat crop plants, landscapes andornamentals, trees and pastures. They can also be used in forestryapplications and on golf courses, to name a few examples. Crop plantsinclude, for example, vegetable crops such as broccoli, cabbage, kale,spinach, onions and peppers; legumes such as beans, lentils, peas andsoybeans; grain crops such as wheat, corn, barley, rye, rice and oats;flower crops such as roses, tulips, daisies, daffodils, gerbera,sunflowers, orchids, jasmine and carnations; root crops such aspotatoes, beets, turnips, parsnips, radishes and carrots. Crop plantscan further include fruits such as citrus, apples, tomatoes, grapes,watermelons, pears, raspberries, blueberries, plums, peaches, bananas,pineapples, strawberries, plantains, kiwis and mangoes; nut trees suchas almonds, chestnuts, hazelnuts, hickory nuts, macadamia nuts, pecans,pine nuts, pistachios and walnuts. The agricultural compositions canalso be applied to and used to treat pastures, such as clover, alfalfaand grasses, and crop plants such as squashes, tubers, zucchini,pumpkins as well as coconut, palm and cacao trees.

The agricultural compositions of this invention can be combined withherbicides and applied to and used to control weeds such as those listedbelow: Anoda (Anoda cristata), Balsamapple (Momordica charantia), Barley(Hordeum vulgare), Barnyardgrass (Echinochloa crus-galli), Bassia(Bassia hyssopifolia), Bittercress (Cardamine spp.), Bluegrass (Poabulbosa), Brome (Bromus tectorum), Japanese brome (Bromus japonicas),Buttercup (Ranunculus spp.), Carolina foxtail (Alopecurus carolinianus),Carolina geranium (Geranium carolinianum), Castorbean (Ricinuscommunis), Chamomile (Anthemis cotula), Cheat (Bromus secalinus),Chervil (Anthriscus cerefolium), Chickweed (Cerastium vulgatum),Cocklebur (Xanthium strumarium), Coreopsis (Coreopsis tinctoria),Volunteer corn (Zea mays), Crabgrass (Digitaria spp.), Dwarfdandelion(Krigia virginica), Eastern mannagrass (Glyceria spp.), Eclipta (Ecliptaprostrata), Falsedandelion (Pyrrhopappus carolinianus), Falseflax(Camelina microcarpa), Fiddleneck (Amsinckia spp.), Field pennycress(Thlaspi arvense), Annual Fleabane (Erigeron annuus), Hairy fleabane(Conyza bonariensis), Rough fleabane (Erigeron strigosus), Floridapusley (Richardia scabra), Foxtail (Setaria spp.), Jointed goatgrass,(Aegilops cylindrical), Goosegrass (Eleusine indica), Common groundsel(Senecio vulgaris), Henbit (Lamium amplexicaule), Horseweed (ConyzaCanadensis), Itchgrass (Rottboellia cochinchinensis), Johnsongrass(Sorghum halepense), junglerice (Echinochloa colona), knotweed(Polygonum spp), kochia (Kochia scoparia), lambsquarters, (Chenopodiumalbum), medusahead (Taeniatherum caput-medusae), morningglory (Ipomoeaspp.), mustard, blue (Chorispora tenella), mustard, tumble (Sisymbriumaltissimum), mustard, wild (Sinapis arvensis), oats, wild (Avena fatua),panicum, fall (Panicum dichotomiflorum), pigweed, redroot (Amaranthusretroflexus), pigweed, smooth (Amaranthus hybridus), prickly lettuce(Lactuca serriola), puncturevine (Tribulus terrestris), purslane, common(Portulaca oleracea), ragweed, common (Ambrosia artemisiifolia),ragweed, giant (Ambrosia trifida), rocket, London (Sisymbrium irio),Russian-thistle (Salsola tragus), rye, cereal (Secale cereal), ryegrass,Italian (Lolium perenne), sandbur, field (Cenchrus spinifex), sesbania,hemp (Sesbania herbacea), shattercane (Sorghum bicolor),shepherd's-purse (Capsella bursa-pastoris), sicklepod (Sennaobtusifolia), signalgrass, broadleaf (Urochloa platyphylla), smartweed(Pennsylvania Polygonum pensylvanicum), sowthistle, annual (Sonchusoleraceus), Spanish needles (Bidens bipinnata), speedwell, corn(Veronica arvensis), speedwell, purslane (Veronica peregrina),sprangletop (Leptochloa spp.), spurge, annual (Chamaesyce spp.), spurge,prostrate (Chamaesyce humistrata), spurge, spotted (Chamaesycemaculate), spurry, umbrella (Holosteum umbellatum), stinkgrass(Eragrostis cilianensis), sunflower, common (Helianthus annuus),tansymustard, pinnate (Descurainia pinnata), teaweed/sida, prickly (Sidaspinosa), Texas panicum (Panicum spp.), velvetleaf (Abutilontheophrasti), Virginia pepperweed (Lepidium virginicum), wheat (Triticumaestivum), witchgrass (Panicum capillare), woolly cupgrass (Eriochloavillosa), yellow rocket (Barbarea vulgaris).

Additional plants for receiving application of agricultural compositionsin accordance with the invention include perennials, such as alfalfa,anise/fennel, bluegrass, Kentucky, clovers, dandelions, poison ivy,milkweed, poison-hemlock, thistles and grasses. Trees include alders,aches, beaches, aspens, cherries, elderberries, elms, hickories,honeysuckle, Kudzu, maples, oaks, pines, spruces, sumacs, ferns,creepers and poplars.

EXAMPLES

Aspects and attributes of preferred embodiments of the invention will bedescribed with reference to the following examples, which are beingpresented for purposes of illustration only and should not be construedas limiting. In addition, unless otherwise indicated, as used in theseexamples, each of R¹ to R¹⁰ can be considered to be methyl.

Product Descriptions

Tables 1-4 describe the products used in the examples that follow.

TABLE 1 Organomodified Polysiloxanes M.W. Viscosity ID Formula x, y, zand w R (g/mol) (cSt) OSIL-1 M¹D_(x)D¹ _(y)M² x = 8, y = 0 R¹ to R⁸ =CH₃ 770 5 z = 0, w = 0 OSIL-2 M¹D_(x)D¹ _(y)M² x = 15, y = 0 R¹ to R⁸ =CH₃ 1250 10 z = 0, w = 0 OSIL-3 M¹D_(x)D¹ _(y)M² x = 25, y = 0 R¹ to R⁸= CH₃ 2000 20 z = 0, w = 0 OSIL-4 M¹D_(x)D¹ _(y)M² x = 49, y = 0 R¹ toR⁸ = CH₃ 3800 50 z = 0, w = 0 OSIL-5 M¹D_(x)D¹ _(y)M² x = 10, y = 5 R¹to R⁹ = CH₃ 1846 47 z = 0, w = 0 R¹⁰ = C₈H₁₇ OSIL-6 M¹D_(x)D¹ _(y)M² x =10, y = 5 R¹ to R⁹ = CH₃ 2126 * z = 0, w = 0 R¹⁰ = C₁₂H₂₅ OSIL-7M¹D_(x)D¹ _(y)M² x = 10,y = 0 R¹, R², R⁴, R⁵ = 1132 * z = 0, w = 0 CH₃R³, R⁶ = C₈H₁₇ OSIL-8 M¹D_(x)D¹ _(y)M² x = 10,y = 0 R¹, R², R⁴, R⁵ =1245 * z = 0, w = 0 CH₃ R³, R⁶ = C₁₂H₂₅ OSIL-9 TS¹R¹¹TS² R^(a) and R¹²to R¹⁷= 587 * CH₃ R¹¹ = C₈H₁₆ OSIL-10 R¹⁹-[—Si(CH₃)₂O_(1/2)-(D²)z- x =0, y = 0 R¹⁹ = H 2884 * Oi/₂Si(CH₃)₂-R¹⁸-]w- R²⁰ z = 10, w = 2 R¹⁸ =C₈H₁₇ R²⁰ = —Si(CH₃)₂O_(1/2)- (D²)z- O_(1/2)Si(CH₃)₂H R²¹, R²² = CH₃ * -Not measured

TABLE 2 Organic Surfactants Designation in the Surfactant ExamplesDescription Vendor Tergitol 15-S-3 NIS-1 Alcohol Ethoxylate Dow Tergitol15-S-5 NIS-2 Alcohol Ethoxylate Dow Tergitol TMN-3 NIS-3 AlcoholEthoxylate Dow Lutensol XL-50 NIS-4 Alcohol Ethoxylate/ BASF PropoxylateEcosurf EH-3 NIS-5 Alcohol Ethoxylate Dow Rhodasurf TR-5 NIS-6 AlcoholEthoxylate Solvay Lumulse CO-5 NIS-7 Castor Oil Ethoxylate VantageTriton X-100 NIS-8 Octylphenol ethoxylate Dow

TABLE 3 Organosilicone-containing Adjuvants Organosil- Designation iconein the surfactant Examples Description Vendor Silwet 641 OSS-1 Blend ofNonionic Momentive Surfactant and Siloxane Polyalkyleneoxide CopolymerSurfactant Y OSS-2 Blend of Nonionic Momentive Surfactant and SiloxanePolyalkyleneoxide Copolymer

TABLE 4 Crop Oil Sources and Type Designation in the Crop oil ExamplesDescription Vendor Orchex 796 MO-1 Mineral Oil Calumet Parol 80 MO-2Mineral Oil Penreco Spray Oil 13 MO-3 Mineral Oil Petro-Canada CA 3040MS-1 Methylated Chemical Soybean Oil Associates Methyl MS-2 MethylatedCargill Soyate Soybean Oil

Spreading Determination

The spreading ability of various compositions and formulations wereevaluated by depositing a single drop (10 microliters) of emulsion (orother material) to be evaluated onto a clean, flat, polystyrene dish.The diameters of the resulting drops were then measured after 30seconds. Each solution was tested 2 to 4 times and the average diameterwas calculated. Alternatively, the spreading ability was also evaluatedby depositing a single drop (10 microliters) of the sample to beevaluated onto a leaf surface. The area of the resulting drops was thenmeasured after 3 minutes, unless otherwise specified. Each sample wastested 2 to 4 times and the average spread area was calculated.

Effect of PDMS Oils on Surface Tension when Blended with Oil Base Stocks

Low surface tension is beneficial to agricultural pesticide applicationsbecause it correlates with better droplet adhesion and spreading. Theeffect of polydimethylsiloxane (PDMS) oils on surface tension whenblended with different oil base stocks was evaluated and the results aredisplayed in FIGS. 1, 2, and 3, which are log scales, such that astraight line actually indicates non-linear results. Thus, the resultsdemonstrated that the addition of small amounts of silicone oil resultedin a disproportionately large reduction in equilibrium surface tension.

As can be seen in FIG. 1, the surface tension of the oil MO-1 droppedfrom 30 to 26 mN/m (more than 10% reduction) with the addition of only1% of OSIL-2, a 10 cSt polydimethyl siloxane (PDMS) oil, identified asElement 14 10A, with an equilibrium surface tension of just below 20.The addition of only 10% OSIL-2 silicone oil reduced the surface tensionof the blend more than half of the difference in surface tensions (30and 20) to 23 mN/m. As used herein, all percentages are calculated on aweight basis. Similarly, as shown in FIG. 2, the addition of 10% (by wt)of OSIL-1, a 5 cSt PDMS oil, to MO-1 reduced the product's equilibriumsurface tension from 29.1 mN/m to 24.3 mN/m. The addition of 10% (by wt)OSIL-3, a 20 cSt PDMS oil, to MO-3 resulted in a reduction in theproduct's surface tension from 30 mN/m to 22.8 mN/m.

FIG. 3 shows that the addition of a low molecular weight silicone oil,OSIL-2, to an esterified seed oil, MS-1, also results in largereductions in surface tension with relatively small amounts of siliconeoil. The addition of 1% OSIL-1 reduced surface tension of the methylsoyate from about 30 mN/m to about 26 and 10% reduced it to about 23mN/m.

Crop oil concentrates (COCs) were formulated to evaluate the effect oflow molecular weight, low viscosity PDMS oils in accordance with theinvention on their foliar spreading and dynamic surface tension. Thesurfactant mixture SURF-1, defined in Table 5, was used in each of theformulations. A commercially available nonionic surfactant, Tergitol®15-S-5, was added to two of the samples to increase the HLB value of thesurfactant package. Tergitol® 15-S-3 and Tergitol® 15-S-5 are the 3 and5 mole ethoxylates respectively of a mixture of C11-C15 secondaryalcohols. Tergitol® TMN-3 is a 3 mole ethoxylate of trimethylnonylalcohol. The results are summarized in Table 6.

TABLE 5 Surfactant Formulation Base Stock (SURF-1) Component Wt % NIS-146.70 1-decanol 20.00 1-dodecanol 20.00 NIS-3 13.30

The data in Table 6 show that the addition of a PDMS oil (OSIL-2) inaccordance with the invention to crop oil concentrate (COC) formulationssurprisingly led to significant and sometimes very large increases inspreading on both poinsettia and philodendron leaves. This wassurprising because the spreading of COC or MSO dispersions is typicallydriven by the surface tension of the aqueous phase of the sprayeddroplet, not the equilibrium surface tension of the dispersed oil phase.The dynamic surface tension curves (DSTs) of the aqueous sprayedsolutions, shown in FIG. 4, of SIL-1 through SIL-5 were all essentiallythe same, and all were significantly lower than the DST curve of theCOC-1 dispersion. Thus, we expected SIL-1 through SIL-5 to give similarspread areas on the plant leaves, and expected all 5 to spreadsignificantly more than the COC-1 dispersion. As expected, the COC-1dispersion was the least effective spreader. However, surprisingly, theformulations containing the polysiloxane OSIL-2 all spread significantlybetter than their counterparts containing no silicone oil.

A benchmark crop oil concentrate, SIL-3, was made by blending 11.25% ofthe SURF-1 surfactant package into MO-1. In SIL-1, 10% OSIL-2 was added,replacing the same amount of MO-1. It can be seen in Table 6 that SIL-1containing OSIL-2 almost doubled the spreading of the SIL-3 benchmark onpoinsettia and increased the spreading on philodendron leaves by 12.5percent.

A second benchmark COC formulation, SIL-5, was formulated. SIL-5contains the SURF-1 surfactant package plus a small amount of surfactantNIS-2 to increase the HLB (hydrophilic to lipophilic balance) of theoverall surfactant package. The polysiloxane OSIL-2 was added to thisformulation to make COC formulation SIL-2. SIL-4 is a similarformulation that contains SURF-1, NIS-2 and OSIL-2. It can be seen inTable 6 that the polysiloxane-containing formulations SIL-2 and SIL-4show 7.6 to 8 times more spreading on poinsettia leaves and 1.7 to 3.6times more spreading on philodendron leaves than is achieved with SIL-5,the benchmark containing no polysiloxane oil.

TABLE 6 Effect of Silicone Oils on Leaf Coverage Average spread area at1.0% on plant leaves DST at 100 mS¹ SURF-1 NIS-2 OSIL-2 MO-1 (mm²) for1.0% soln. Sample Wt % Wt % Wt % Wt % Poinsettia Philadendron (mN/m)SIL-1 11.25 0 10.00 78.75 110 63 52 SIL-2 10.98 2.44 9.76 76.83 480 16050 SIL-3 11.25 0 0 88.75 56 56 52 SIL-4 9.20 2.05 10.00 78.75 510 325 52SIL-5 10.98 2.44 0 86.58 63 90 52 COC-1^(‡) 100 0 0 0 20 25 69 ^(‡)COC-1is Agri-Dex from Helena Chemical Co., a commercial benchmark crop oilconcentrateTo summarize, experimental COC formulations SIL-1 through SIL-5 allshowed significantly enhanced spreading when compared to a 1% solutionof COC-1, a commercially available crop oil concentrate. Moreover,whereas the dynamic surface tension curves of SIL-1 through SIL-5 areessentially the same, significantly improved spreading properties wereunexpectedly observed with the formulations containing polysiloxanes.This indicates that the improved spreading was not merely the result ofreduced surface tension, but an unexpected result of the silicone oilsof the invention, especially when combined with the surfactant NIS-2.Thus, the addition of OSIL-2 had no significant effect on the DST(dynamic surface tension) of 1% solutions of these experimental COCs,but an unexpected increase in spreading (see Table 6).

Tables 7 and 8, below, show the effect of different PDMS oils inaccordance with the invention, in combination with differentsurfactants, on foliar spreading in experimental COC formulations. Asshown in these tables, the addition of silicone oils in accordance withthe invention led to significant improvements in spreading with all ofthe surfactants, when tested on philodendron, bamboo, broccoli andpoinsettia leaves. COC formulations SIL-21 and SIL-22 demonstrate thatthe improved spreading seen with the addition of OSIL-2 also occurs whenthe COC is formulated with a different oil base stock, in this caseParol® 80 (MO-2) instead of Orchex® 796 (MO-1).

The largest increases in foliar spreading were seen when the siliconeoil was combined with the surfactants NIS-2 (SIL-7 and SIL-8), NIS-1(SIL 16), NIS-4 (SIL-10) and NIS-6 (SIL-18). The 50 cSt PDMS oil(OSIL-4, Element 14 PDMS 50), used in formulation SIL-8, appeared to beat least as effective as, if not better than OSIL-2, as can be seen whencomparing SIL-7 and SIL-8. However, the higher viscosity silicone oilsare harder to solubilize and/or emulsify in crop oil concentrateformulations.

TABLE 7 Effect of Surfactant and PDMS on COC Spreading (1% dispersions)Spread area (mm²) Surfactant MO-1 Philodendron Bamboo Broccoli Sample(10 wt %) PDMS (10 wt %) (q.s. 100) Appearance Spread Spread SpreadSIL-6 NIS-2 90 Clear 27 20 240 SIL-7 NIS-2 OSIL-2 80 Clear 142 581 705SIL-8 NIS-2 OSIL-4 80 Clear 260 352 1000 SIL-9 NIS-4 90 Hazy 25 28 30SIL-10 NIS-4 OSIL-2 80 Slight haze 45 40 182 SIL-11 NIS-5 90 Hazy 12 1630 SIL-12 NIS-5 OSIL-2 80 Slight haze 20 20 42 COC-1 — — — Clear 11 12 9

TABLE 8 Effect of Surfactant and PDMS on COC Spreading (1% dispersions)Oil Base Spread area of 1% spray Surfactant Stock Emulsion solutionsafter 5 min. (mm²) Sample (10 wt %) OSIL-2 (q.s.100) Appearancestability Philodendron Bamboo Poinsettia SIL-6 NIS-2 Nil¹ 90% Slighthaze opaque/stable 28 23 68 MO-1 SIL-7 NIS-2 10% 80% Clear opaque/stable114 245 211 MO-1 SIL-13 NIS-8 Nil¹ 90% Hazy light 30 26 9 MO-1gray/quick separation SIL-14 NIS-8 10% 80% Hazy light 30 30 16 MO-1gray/quick separation SIL-15 NIS-1 Nil¹ 90% Clear slight 31 23 43 MO-1gray/stable SIL-16 NIS-1 10% 80% Clear slight 118 238 253 MO-1gray/stable SIL-17 NIS-6 Nil¹ 90% Slight haze opaque/stable 27 25 68MO-1 SIL-18 NIS-6 10% 80% Slight haze opaque/stable 98 45 107 MO-1SIL-19 NIS-7 Nil¹ 90% Hazy slight 25 21 33 MO-1 gray/stable SIL-20 NIS-710% 80% Hazy slight 48 30 47 MO-1 gray/stable SIL-21 NIS-2 Nil¹ 90%Slight haze opaque/stable 31 16 28 MO-2 SIL-22 NIS-2 10% 80% Clearopaque/stable 142 95 147 MO-2 ¹no added alkyl silicone

The data in Table 9 show that the SIL-23, a COC formulation containingOSIL-1, increased the spreading on bamboo, philodendron and poinsettialeaf surfaces by approximately 3 times when compared to SIL-6, thenon-silicone oil-containing benchmark.

TABLE 9 Effect of OSIL-1 and OSIL-2 on COC Spreading Spread area of 1%spray solutions (mm²) Sample NIS-2 PDMS MO-1 Appearance BambooPhilodendron Poinsettia SIL-6 10% Nil¹ 90% light haze 23 25 49 SIL-2310% 10% OSIL-1 80% Clear 64.0 69 156 SIL-7 10% 10% OSIL-2 80% Clear 24087 81 ¹no added alkyl silicone

Table 10, below, summarizes the results of spreading examples performedwith 0.5% solutions of SIL-6 and SIL-7 (COCs made with MO-1, aparaffinic hydrocarbon oil, Orchex 796, from Calumet SpecialtyChemicals) and SIL-24 and SIL-25 (MSOs made with MS-1, a methyl soyate,CA 3050, from Chemical Associates, A Division of Univar USA, Inc). Withboth base-stocks, the addition of a silicone oil (OSIL-2) in accordancewith the invention significantly improved the foliar spreadingproperties of the product.

TABLE 10 Spreading of 0.5% COC spray solutions Emulsion Leaf Wettingarea (mm²) of 0.5% 10% 10% Appearance stability Solutions^(‡) SampleMO-1 MS-1 NIS PDMS (neat) (0.5%)*^(‡) Philodendron Bamboo Broccoli SIL-690 NIS-2 Clear 5 20.0 27.0 96.0 30.0 20.0 75.0 SIL-7 80 NIS-2 OSIL-2clear 5 130.0 96.0 103.5 112.0 108.0 140.0 SIL-24 90 NIS-2 clear 5 30.027.5 80.0 SIL-25 80 NIS-2 OSIL-2 clear 5 117.0 48.0 96.0 COC-1 clear 99.0 9.0 7.5 *10 is opaque/milky white and very stable, 1 is almost clearwith rapid separation *Dispersibility of the 0.5% emulsion was quitegood considering the low concentration ^(‡)Except for COC-1 (Agri-Dex),which was tested at 1.0%

Table 11 summarizes the results of spreading examples performed with1.0% solutions of formulation containing OSIL-3, a 20 cStpolydimethysiloxane (PDMS) oil and NIS-2 in two different mineral oils(MO-1 and MO-3). SIL-6 and SIL-7 were used as benchmarks for formulationSIL-26. All three of these products are based on MO-1. FormulationSIL-27 was used as a benchmark for SIL 28. Both of these products arebased on MO-3. With both oil base-stocks, the addition of a silicone oilin accordance with the invention significantly improved the foliarspreading properties of the product when compared to the same mineraloil containing only the nonionic surfactant NIS-2.

TABLE 11 Effect of OSIL-1 and OSIL-3 on COC Spreading Spread area of 1%spray solutions (mm²) Sample NIS-2 PDMS Oil Base Stock Appearance BambooPhilodendron Poinsettia SIL-6 10% Nil¹ 90% MO-1 light haze 25 33.5 80.5SIL-7 10% 10% OSIL-2 80% MO-1 clear 158 77 110 SIL-26 10% 10% OSIL-3 80%MO-1 clear 115 168 210 SIL-27 10% Nil¹ 90% MO-3 clear 25 35 172 SIL-2810% 10% OSIL-3 80% MO-3 Clear 145 150 470 ¹no added alkyl silicone

Adhesion tests performed with 0.5% aqueous solutions of Sil-6 and SIL-7demonstrated the significant enhancement of the adhesion of formulationsin accordance with the invention to foliage. Solution droplets weregenerated using a syringe pump and a Nisco Encapsulation Unit (Var J1)J1 employing a nozzle with an inner diameter of 0.41 mm. The data inTable 12 show that the addition of a the PDMS oil OSIL-2 to the COCformulation (SIL-6) increased the number of drops that adhered to thegrass leaf surface approximately threefold, from 16.3 percent (SIL-6) to45.9 percent (SIL-7). As can be seen in FIG. 10, both of these COCformulations presented essentially the same dynamic surface tension.Therefore, based on the understanding that droplet adhesion increaseswith decreasing dynamic surface tension (DST), the enhanced adhesionresults seen here were unexpected.

TABLE 12 Droplet Adhesion on Barnyardgrass (Echinochloa crus-galli)Conc. Average Sample Composition (%) % Adhesion Stdev % DI Water — 3.12.7 SIL-6 10% NIS-2 0.5 16.3 11.4 90% MO-1 SIL-7 10% NIS-2 0.5 45.9 12.480% MO-1 10% OSIL-2 water drop size ≈ 950 μm COC drop size ≈ 700 μm dropfall distance = 49.5 cm drop impact velocity ≈ 2.5-3 m/s

A similar droplet adhesion study was performed using a methylated seedoil (MSO) formulation, both with and without OSIL-2 (SIL-24 and SIL-25respectively). Droplets of approximately 400 μm in diameter weregenerated at a height of 53 cm above a cabbage leaf surface. The leaveswere mounted on a 22.5° slope. The percentage of impacted drops thatadhered to the cabbage leaf surface was then determined. As was the casewith the petroleum oil (mineral oil) based COCs in Table 12, theaddition of silicone oil to the MSO unexpectedly and greatly improvedthe adhesion of the droplets onto the surface of a cabbage leaf. Theresults are summarized in Table 13, below.

TABLE 13 Adhesion of Adjuvant Solutions on the Cabbage Adaxial LeafSurface Adjuvant Conc. Adhesion treatment Description % w/v % COC-1Agri-Dex 0.5 47 SIL-24 90% MS-1, 10% NIS-2 0.5 51 SIL-25 80% MS-1, 10%NIS-2, 10% OSIL-2 0.5 74 Adhesion mean differences were statisticallysignificant with 95% confidence (P0.05, LSD test).

Referring to Table 14, below, Silwet 641 (OSS-1) is a surfactant mixturebased on a superspreader (trisiloxane alkoxylate) organosilicone andsome nonionic surfactants. It is typically added to an MSO base stock atconcentrations ranging from 10 to 20 percent. Sample SIL-29 in Table 14is a blend of 20 wt % OSS-1 and 80 wt % MS-1. Sample SIL-30 is a blendcontaining 20 wt % OSS-1, 70 wt % MS-1 and 10 wt % OSIL-2. Silwet 641 isoften referred to as a superspreader and it has been believed to providethe best spreading properties obtainable. The data in Table 14 and FIGS.5 and 6 demonstrate that the addition of the silicone oil in accordancewith the invention lowered the equilibrium surface tension, increasedthe emulsion stability of the MSO concentrate to which it was added, andsurprisingly increased the spread diameter of the product. Note that inFIG. 6, TSI measures emulsion separation, such that a lower TSIcorresponds to increased emulsion stability.

TABLE 14 Blends of PDMS, Nonionic & Organosilicone Surfactants in MSOSpread Diameter OSS-1 OSIL-2 MS-1 EST at 0.5% at 0.5% Sample (wt %) (wt%) (wt %) (mN/m) (mm) SIL-29 20 0 80 22.9 31.0 SIL-30 20 10 70 22.5 33.9

A similar study was performed by adding a silicone oil to an MSOadjuvant formulation and evaluating the product's spray coverage.Instead of measuring the spread diameter over a hydrophobic surface, adozen sprays were performed with 0.5% spray solutions of samples SIL-31and SIL-32. The solutions were sprayed at a pressure of 20 psig using aUnijet® 8002E flat-fan nozzle. These spray conditions equate to a fieldspray volume of 100 L/ha. The coverage achieved on a square of watersensitive paper was determined for each spray. The average spraycoverage for each product was then calculated. The results aresummarized in Table 15. The data show that an increase in spray coveragewas achieved through the addition of low molecular weight silicone oil(polysiloxane) in accordance with the invention to the MSO formulationwith SIL-32 (with OSIL-2) providing better coverage than the SIL-31 thatcontains no PDMS oil.

TABLE 15 Spray Coverage of Surfactant Blends in MSO Adjuvants Averagecovered OSS-1 OSIL-2 MS-2 area (%) with 0.5% Sample (wt %) (wt %) (wt %)spray solutions SIL-31 20 0 80 47.3 SIL-32 20 20 60 52.1

The impact of the compositions of the present invention on dropletadhesion of spray solutions was tested on difficult-to-wet barnyardgrass(Echinochloa crus-galli), following the methodology previously describedby Gaskin et al. (Stevens, P J, Kimberley, M O, Murphy, D S, &Policello, G A; Adhesion of spray droplets to foliage: the role ofdynamic surface tension and advantages of organosilicone surfactants,Pesticide Science, Vol. 38, 1993, pp. 237-245. Forster, W A, Mercer, G Nand Schou, W C, Process-driven models for spraydroplet shatter, adhesionor bounce, In: Baur P, Bonnet M, editors. Proceedings 9th InternationalSymposium on Adjuvants and Agrochemicals. ISAA978-90-815702-1-3; 2010).Droplets with a diameter ca. 400 μm were impacted from a height of 53cm, to leaves mounted at 22.5 degrees from horizontal. The dropletadhesion was compared to the dynamic surface tension of the respectiveformulations. The composition of samples SIL-33 through SIL-36 are shownin Table 16.

TABLE 16 Preparation Examples of Agricultural Deposition Aids ComponentsSIL-33 SIL-34 SIL-35 SIL-36 AgroSpred 820 100.00 OSS-2 20.00 20.00 20.00OSIL-2 10.00 10.00 d-limonene 20.00 MS-1 80.00 70.00 50.00 Total 100.00100.00 100.00 100.00 AgroSpred 820 is a MSO concentrate made of 20 wt %Silwet 641 and 80% MS-1

The barnyard grass adaxial leaf surface is extremely difficult to wet.Therefore, this is a good target for comparative droplet adhesionstudies. Table 17 gives the droplet adhesion reported as the percentageof impacted droplets retained on the leaf surface. As can be seen inTable 17, the compositions of the present invention gave an unexpectedlylarge increase in droplet adhesion relative to the commercial benchmarkAgroSpred 820 (20 wt % Silwet 641, 80 wt % MSO) and relative to theSIL-34 benchmark that contains no PDMS oil. This unexpected improvementis associated with the use of the 10 cSt PDMS oil OSIL-2. The level ofimprovement, exceeding a twofold increase in droplet adhesion, is asurprising and unexpected result given the small to insignificantdifferences observed in the DST at typical impact times (between 50 and250 milliseconds).

TABLE 17 Adhesion of Adjuvant Treatments on Barnyardgrass (BYDG)Foliage. Surface Tension as a function of Interface Development TimeAdjuvant Conc. 50 100 250 Adhesion (%) treatment (%) msec msec msec onBYDG SIL-33 0.5 47.2 44.3 40.8 25 SIL-34 0.5 49.0 46.2 41.1 12 SIL-350.5 49.0 45.5 39.6 54 SIL-36 0.5 51.7 47.0 41.8 62

Also tested was the effect of low MW PDMS oil on the foam volume of MSOconcentrates. FIG. 7 shows the foam volume determined by a sparge test.In this test, nitrogen is bubbled in the spray solution employing ametal frit at a rate of 1.0 L/min for 1 min. The foam volume is measuredat initial (point at which bubbling stops), 1, 2, 5 and 10 minutes. Ascan be seen, the low MW PDMS oil reduced the foam levels below what canbe achieved with the use of a high-performance antifoam (e.g., SAG-1572available from Momentive Performance Materials). This result wasunexpected because the presence of trisiloxane alkoxylates typicallyrender commercial antifoams ineffective at typical use rates, a resultassociated with the low equilibrium surface tension delivered byorganosilicone superspreaders.

As described above the addition of low concentrations (1-20%) of lowmolecular weight, low viscosity polydimethylsiloxanes (silicone oils) inaccordance with the invention to COCs and MSOs significantly reduced thesurface tension of the petroleum oil and seed oil base stocks. Thepresence of the silicone oil also enhanced the adhesion of the sprayedCOC and MSO droplets to foliar surfaces. Furthermore, the addition ofthese low molecular weight silicone oils to the crop oil concentrate andMSOs unexpectedly led to much improved spreading on a variety of leafsurfaces, while also improving the emulsion stability and reducing thefoam volume.

Note that a limiting factor can be the poor solubility of the PDMS oilsin the crop oil-base stocks. The results below describe examination ofthe effect of a variety of alkyl-silicone oils on the performance ofCOCs and MSOs. All of the alkyl-silicone oils evaluated here showed goodsolubility in both mineral oils and methylated seed oils andsignificantly reduced the equilibrium surface tension of the resultingCOCs and MSOs. Additionally, all of the alkyl-silicone oils enhanced thespreading of the COCs and MSOs on plant leaves. The tested alkylmodified silicones are set forth below.

Alkyl Modified Silicones. The Alkyl Groups are Either C8 or C12.

The solubility of the alkyl silicone oils in a typical mineral oil and amethylated seed oil were first determined. The effect of thealkyl-silcones on the equilibrium surface tension of blends with thecrop oil base stocks was then measured. Finally, the spreadingcharacteristics of simple COC and MSO formulations containing the alkylmodified silicone oils were determined.

OSIL-5, OSIL-6, OSIL-7 and OSIL-8 all exhibited good solubility in MO-1.The equilibrium surface tension of these neat alkyl silicone oils wasthen determined. They had surface tensions of between 22 and 23 mN/m(see Table 18), which is significantly lower than the surface tension ofneat MO-1, which is 29.9 mN/m.

The effect of alkyl silicone concentration on the equilibrium surfacetension of MO-1 was determined. The addition of 10% OSIL-5 to MO-1resulted in a significant surface tension reduction, from 29.9 toapproximately 26 mN/m. For OSIL-6 through OSIL-8, the addition of 10% ofalkyl silicone to MO-1 reduced the surface tension to below 24 mN/m.This is similar to the surface tension reduction achieved when addingOSIL-2 to MO-1. It was observed that even though the compositions of thepresent invention are able to reduce the equilibrium surface tension ofthe neat oil blends, such reduction was not always observed for theaqueous dispersions of the respective oil-based formulations.Additionally, no significant variation is observed in the dynamicsurface tension (DST) of the spray solutions containing COCs or MSOswith and without the compositions of the present invention. One skilledin the art would expect the droplet adhesion of those formulations to beequivalent since droplet adhesion usually correlates with dynamicsurface tension; however, the incorporation of the compositions of thepresent invention gave increased droplet adhesion even though there wasno significant reduction in DST. This observation was unexpected andsurprising. Data for solubility of alkyl silicones in MSO and ESTdeterminations are summarized in Table 18. Surface tension vs. alkylsilicone concentration curves are shown in FIG. 8.

TABLE 18 Solubility and Equilibrium Surface Tension of Alkyl-Silicone inMSO EST of MO-1 blends (the percentage EST indicates the amount of alkylsilicone in Alkyl neat wt %, MO-1 qs 100) silicone Solubility at 10% inMO-1 (mN/m) 1.0 wt % 4.8 wt % 9.2 wt % 16.8 wt % OSIL-5 clear, colorlesssolution, no 22.9 27.4 26.9 26.5 25.6 separation OSIL-6 clear, colorlesssolution, no 22.6 27.8 25.3 23.9 23.0 separation OSIL-7 clear, colorlesssolution, no 22.2 25.3 24.3 24.0 23.8 separation OSIL-8 clear, colorlesssolution, no 22.6 26.3 24.7 23.9 23.7 separation

Samples of crop oil concentrates (COCs) based on MO-1 and 10% of thenonionic surfactant NIS-2 were formulated to determine the effect of thealkyl silicones, in accordance with the invention, on spreading. A 10:90blend of surfactant in oil was used as a benchmark. The COC formulationsand the spreading of 1 percent dispersions of these products are shownin Table 19. All of the COC formulations containing alkyl silicone oilsspread significantly better than the NIS-2/MO-1 control (SIL-41) onphilodendron and bamboo leaves.

TABLE 19 Effect of Alkyl Silicones on the Spreading of NIS-2/MO-1 Blends(1% dispersions) Alkyl Spread Area (mm²) MO-1 NIS-2 siliconePhilodendron Philodendron Bamboo Bamboo Sample (wt %) (wt %) (10% wt)After 15 min After 80 min After 15 min After 80 min SIL-37 80 10 OSIL-538 38 25 41 SIL-38 80 10 OSIL-6 43 40 25 35 SIL-39 80 10 OSIL-7 70 80 5876 SIL-40 80 10 OSIL-8 72 86 45 56 SIL-41 90 10 — 27 30 24 27

A similar set of data was generated to see how these four alkylsilicones behaved in MS-1. Table 20 shows the solubility and equilibriumsurface tension of the alkyl-silicones blended with MS-1. All fourproducts exhibited good solubility in the methyl soyate base oil. Theeffect of different concentrations of alkyl silicones OSIL-6 and OSIL-7on the equilibrium surface tension of MS-1 was determined and both alkylsilicones reduced the surface tension of CA-1 by more than 5 mN/m at aconcentration of 10 percent.

TABLE 20 Solubility and Equilibrium Surface Tension of Alkyl-Siliconesin MS-1 Alkyl- Solubility at 10% in ST (neat) EST (mN/m) at X % in MS-1silicone MS-1 mN/m 1% 5% 10% 20% OSIL-6 clear, light yellow, 22.6 25.925.4 23.7 22.6 no separation OSIL-7 clear, light yellow, 22.2 25.4 24.523.3 22.9 no separation Nil¹ — 29.9 — — — — ¹MS-1 with no alkyl-siliconeoil

Methylated seed oil concentrates (MSOs) based on MS-1 were prepared.They contained 10 wt % NIS-2, 10 wt % alkyl silicone, and 80 wt % MS-1.A 10:90 blend of surfactant NIS-2 in seed oil MS-1 was used as abenchmark. The MSO formulations and the spreading of 1 percentdispersions of these products are shown in Table 21. Both of the MSOformulations containing alkyl silicones spread significantly better thanthe SIL-44 benchmark after 15 and 120 minutes of spreading. (except forthe SIL-42 dispersion which was equivalent to the control onphilodendron after 2 hours).

TABLE 21 Effect of Alkyl Silicones in the Spreading of NIS-2/MS-1 Blends(1% dispersions) Alkyl Spread Area (mm²) MS-1 NIS-2 siliconePhilodendron Philodendron Bamboo Bamboo Sample (wt %) (wt %) (10% wt) 15min 120 min 15 min 120 min SIL-42 80 10 OSIL-6 36 46 37 49 SIL-43 80 10OSIL-7 36 72 25 132 SIL-44 90 10 none 20 46 20 28

Table 22 shows the effect of OSIL-9 and OSIL-10 on the equilibriumsurface tension of MO-1. Both of these alkyl-silicones significantreduce the surface tension of the oil at relatively low concentrations.

TABLE 22 Equilibrium Surface Tension of blends of MO-1 with AlkylSilicones Equilibrium Surface Tension (mN/m) Alkyl Solubility at at X %in MO-1 silicone 10% in MO-1 0% 1% 5% 10% 20% 100% OSIL-9 clear,colorless 29.9 29.1 25.4 25.2 23.7 21.7 solution, no separation OSIL-10clear, colorless 29.9 24.0 23.4 23.5 22.5 21.8 solution no separation

Samples of a crop oil concentrate containing OSIL-9 and OSIL-10 weremade up. A 10:90 blend of NIS-2 in MO-1 was again used as a benchmark.The spreading of 1 percent dispersions of these products was determinedon polystyrene plates, philodendron leaves and bamboo leaves. Theresults are summarized in Table 23. The composition of this invention,SIL-45, gave very superior spreading to the benchmark sample, SIL-47.SIL-46, also a composition of this invention, showed significantlybetter spreading than the SIL-47 benchmark on the leaf surfaces.

TABLE 23 Effect of alkyl Silicones in the Spreading of NIS-2/MO-1 Blends(1% dispersions) Alkyl Spread Area (mm²) MO-1 NIS-2 silicone PolystyrenePhilodendron Philodendron Bamboo Bamboo Sample (wt %) (wt %) (10% wt) 30sec 15 min 2 hrs 15 min 2 hrs SIL-45 80 10 OSIL-9 40 38 38 42 42 SIL-4680 10 OSIL-10 90 96 182 210 164 SIL-47 90 10 Nil¹ 45 30 30 25 34 ¹noadded alkyl silicone

OSIL-9 and OSIL-10 were also evaluated in MS-1. Both products exhibitedgood solubility in the seed oil. The effect of different concentrationsof these two alkyl silicones on the equilibrium surface tension of themethyl soyate was determined and are shown in Table 24.

TABLE 24 Equilibrium Surface Tension of Blends of MS-1 with AlkylSilicones Surface Alkyl Solubility at 10% in Tension (neat) SurfaceTension (mN/m) at X % in MS-1 silicone MS-1 (mN/m) 0% 1% 5% 10% 20% 100%OSIL-9 clear, light yellow 21.7 30.2 28.4 29.2 24.6 22.6 21.7 fluid, noseparation OSIL-10 clear, light yellow 21.8 30.2 24.9 24.4 24.0 23.921.8 fluid, no separation

An MSO concentrate was formulated with 10 wt % NIS-2, 10 wt % OSIL-10and 80 wt % MS-1. A 10:90 blend of the NIS-2 surfactant in seed oil MS-1was used as a control. The formulations and the spreading of 1 percentdispersions of these products are shown in Table 24. The alkyl-siliconecontaining formulation, SIL-48, gave very good spread on all surfacestested and was far superior than the control formulation, SIL-49.

TABLE 25 Effect of Alkyl Silicones in the Spreading of NIS-2/MS-1 Blends(1% dispersions). Alkyl Spread Area (mm²) MS-1 NIS-2 siliconePolystyrene Philodendron Philodendron Bamboo Bamboo Sample (wt %) (wt %)(10% wt) 30 sec 15 min 2 hrs 15 min 2 hrs SIL-48 80 10 OSIL-10 50 42 6435 126 SIL-49 80 10 Nil¹ 13 11 25 36 84 ¹no added alkyl silicone

FIG. 9 shows the droplet adhesion of some of the compositions of thepresent invention tested on poinsettia leaves. Results are expressed asthe average percent of impacting droplets that were retained over theleaf surface. As can be seen, the compositions of the present inventiondeliver a significantly higher droplet deposition rate than thebenchmark COC formulation.

The following examples comprise alkyl silicones in MSO formulationscontaining organosilicone superspreaders. The MSO samples that wereevaluated consisted of 70 wt % MS-1, 20 wt % OSS-1, and 10 wt % of thealkyl modified silicones. These MSO compositions are described in Table26. Table 26 also shows the effect of the alkyl silicones on the foamvolume of seed oil concentrates containing organosiliconesuperspreaders. As can be seen, the composition of the present inventiondelivers lower foam volumes when combined with organosliconesuperspreaders in seed oil concentrates.

TABLE 26 Effect of Alkyl Silicones on the Foam Volume (sparge test) ofMethylated Seed Oil Concentrates Containing OrganosiliconeSuperspreaders. Alkyl MS-1 OSS-1 silicone Foam volume Sample (wt %) (wt%) (10% wt) 0 min 1 min 2 min 5 min 10 min AgroSpred 820 80 20 — 11001020 1000 980 900 SIL-50 70 20 OSIL-5 1110 1080 1040 940 500 SIL-51 7020 OSIL-6 1110 1020 980 900 500 SIL-52 70 20 OSIL-7 1090 1000 960 900550 SIL-53 70 20 OSIL-8 1150 1060 1040 920 500 SIL-54 70 20 OSIL-9 11101040 960 780 220 SIL-55 70 20 OSIL-10 1110 1050 950 800 250

While the invention has been described with reference to particularembodiments, those skilled in the art will understand that variouschanges may be made and equivalents may be substituted for elementsthereof without departing from the scope of the invention. It isintended that the invention not be limited to the particular embodimentsdisclosed, but that it include all embodiments falling within the scopeof the appended claims.

What is claimed is:
 1. An organosilicone-based agricultural composition,comprising a combination of (a) an oil component, (b) a surfactant; and(c) a polysiloxane having an average molecular weight of about 4,000g/mole or lower and a viscosity of about 50 cSt or lower at 25° C.,wherein the polysiloxane is soluble or dispersible in the oil component.2. The agricultural composition of claim 1, wherein about 5% to 95% ofthe composition comprises the oil component, about 1% to 50% of thecomposition comprises the surfactant; and about 1% to 95% of thecomposition comprises the polysiloxane component.
 3. The agriculturalcomposition of claim 1, wherein the combination will exhibit at least50% improved spreading or 50% improved deposition to a leaf surface thanthe same composition will spread or adhere to the leaf in the absence ofthe polysiloxane.
 4. The agricultural composition of claim 1, whereinthe oil component is a mineral oil, a paraffinic crop oil, a vegetableoil, or an esterified seed oil and the polysiloxane is apolydimethylsiloxane or an organo-modified polysiloxane.
 5. Theagricultural composition of claim 1, wherein the polysiloxane has thegeneral formula (I):M ¹ D _(x) D _(y) M ²  (I) wherein: M¹=R¹R²R³SiO_(1/2)M²=R⁴R⁵R⁶SiO_(1/2) D=R⁷R⁸SiO_(2/2) D¹=R⁹R¹⁰SiO_(2/2) R¹, R², R³, R⁴, R⁵and R⁶ are independently selected from a monovalent alkyl hydrocarbonradical of 1 to 18 carbons, and aryl or alkaryl hydrocarbon radicals of6 to 14 carbon atoms; R⁷ and R⁸ are independently selected frommonovalent hydrocarbon radicals of 1 to 4 carbons; R⁹ and R¹⁰ areindependently selected from a monovalent hydrocarbon radical of 1 to 18carbons, and aryl or alkaryl hydrocarbon radicals of 6 to 14 carbonatoms; and; subscripts x and y are 0 to 50, and x+y is about 1 to
 50. 6.The agricultural composition of claim 5, wherein x+y is 5 to
 50. 7. Theagricultural composition of claim 5, wherein y=0 and x is 3 to
 50. 8.The agricultural composition of claim 5, wherein R¹ to R⁸ are methyl. 9.The agricultural composition of claim 7, wherein R¹ to R⁸ are methyl.10. The agricultural composition of claim 9, wherein y=0 and x is about5 to
 25. 11. The agricultural composition of claim 1, wherein thepolysiloxane has a viscosity of about 20 cSt or lower at 25° C.
 12. Theagricultural composition of claim 11, wherein the polysiloxane has amolecular weight of about 2,000 g/mole or lower.
 13. The agriculturalcomposition of claim 5, wherein Wand R⁴ are monovalent alkyl hydrocarbonradicals of 1 to 18 carbons, or aryl or alkaryl hydrocarbon radicals of6 to 14 carbon atoms and R², R³, and R⁵ through R¹⁰ are methyl.
 14. Theagricultural composition of claim 12, wherein x+y is 5 to
 50. 15. Theagricultural composition of claim 5, wherein R¹⁰ is a monovalent alkylhydrocarbon radical of 1 to 18 carbons, or an aryl or alkarylhydrocarbon radical of 6 to 14 carbon atoms and R¹ through R⁹ aremethyl.
 16. The agricultural composition of claim 15, wherein x+y is 5to
 50. 17. The agricultural composition of claim 1, comprising a C4 toC18 alcohol alkoxylate surfactant.
 18. The agricultural composition ofclaim 1, and comprising a solvent selected from d-limonene, triacetin,isopropylmyristate, and esterified seed oil.
 19. The agriculturalcomposition of claim 1, and comprising an oil carrier selected from thegroup of petroleum oil, mineral oil, paraffinic mineral oil, vegetableoil, esterified vegetable oil, esterified seed oil.
 20. The agriculturalcomposition of claim 1, wherein the polysiloxane is an alkyl modifiedpolysiloxane having the general formula (II):TS ¹ R ¹¹ TS ²  (II) wherein, TS¹ and TS² are independentlyR¹²R¹³R¹⁴Si—O—SiR¹⁵R¹⁶R¹⁷ wherein Si^(a) is a monovalent radical and R¹¹is attached to Si^(a), R¹¹ is selected from divalent hydrocarbonradicals of 4 to 18 carbons, and R^(A), R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷are independently selected from monovalent hydrocarbon radicals of 1 to4 carbons.
 21. The agricultural composition of claim 1, wherein thepolysiloxane is an alkyl modified polysiloxane having the generalformula (III):R¹⁹—[Si(CH₃)₂O_(1/2)-(D ²)z-O_(1/2)Si(CH₃)₂—R¹⁸]_(w)—R²⁰  (III) whereinR¹⁹=H—, CH₃—, or HR¹⁸— R²⁰=H—, or—Si(CH₃)₂O_(1/2)-(D²)z-O_(1/2)Si(CH₃)₂H or—Si(CH₃)₂O_(1/2)-(D²)_(z)-O_(1/2)Si(CH₃)₂CH₃, R¹⁸ is selected fromdivalent hydrocarbon radicals of 4 to 18 carbons D²=R²¹R²²SiO_(2/2), R²¹and R²² are independently selected from monovalent hydrocarbon radicalsof 1 to 4 carbons, z=2 to 20, and w=1 to
 20. 22. The agriculturalcomposition of claim 1, wherein w is 1 or
 2. 23. A method of increasingthe spreading or adhesion properties of an agricultural compositioncontaining (a) an oil component and (b) a surfactant, comprising addingto the formulation, an amount of a selected polysiloxane ororgano-modified polysiloxane having a molecular weight below about 4,000g/mol, effective to cause the combination to exhibit 10% improvedadhesion or spreading when compared to the same formulation, but in theabsence of the polysiloxane or organomodified polysiloxane.
 24. Themethod of claim 23, wherein the polysiloxane has the general formula:M ¹ D _(x) D ¹ _(y) M ²  (I) wherein: M¹=R¹R²R³SiO_(1/2)M²=R⁴R⁵R⁶SiO_(1/2) D=R⁷R⁸SiO_(2/2) D¹=R⁹R¹⁰SiO_(2/2) R¹, R², R³, R⁴, R⁵and R⁶ are independently selected from a monovalent alkyl hydrocarbonradical of 1 to 18 carbons, and aryl or alkaryl hydrocarbon radicals of6 to 14 carbon atoms, R⁷ and R⁸ are independently selected frommonovalent hydrocarbon radicals of 1 to 4 carbons; R⁹ and R¹⁰ areindependently selected from a monovalent hydrocarbon radical of 1 to 18carbons, and aryl or alkaryl hydrocarbon radicals of 6 to 14 carbonatoms; subscripts x and y are 0 to 50 and x+y is about 1 to 50; orTS ¹ R ¹¹ TS ²  (II) wherein, TS¹ and TS² are independentlyR¹²R¹³R¹⁴Si—O—Si^(a)(R^(A))—O—SiR¹⁵R¹⁶R¹⁷ wherein Si^(a) is a monovalentradical and R¹¹ is attached to Si^(a), R¹¹ is selected from divalenthydrocarbon radicals of 4 to 18 carbons, R^(A), R¹², R¹³, R¹⁴, R¹⁵, R¹⁶and R¹⁷ are independently selected from monovalent hydrocarbon radicalsof 1 to 4 carbons; orR¹⁹—[Si(CH₃)₂O_(1/2)-(D ²)z-O_(1/2)Si(CH₃)₂—R¹⁸]_(w)—R²⁰  (III) whereinR¹⁹=H—, CH₃—, or HR¹⁸— R²⁰=H—, or—Si(CH₃)₂O_(1/2)-(D²)z-O_(1/2)Si(CH₃)₂H or—Si(CH₃)₂O_(1/2)-(D²)_(z)-O_(1/2)Si(CH₃)₂CH₃, R¹⁸ is selected fromdivalent hydrocarbon radicals of 4 to 18 carbons D²=R²¹R²²SiO_(2/2), R²¹and R²² are independently selected from monovalent hydrocarbon radicalsof 1 to 4 carbons, z=2 to 20, and w=1 to
 20. 25. The method of claim 24,wherein the polysiloxane or organomodified polysiloxane has a viscosityof not more than about 50 cSt at 25 degrees C.
 26. An agrochemicalcomposition, comprising a bioactive component and the agriculturalcomposition of claim
 1. 27. A plant having the agrochemical compositionof claim 26 applied thereto.